Preparation of vat dyestuff isomers of the 1.4.5.8 naphthoylene dibenzimidazol series and the product



Patented Nov. 22, 1932 I r omrso ysrAr-aes"PA TENT- [OFFICE l I WILHELMnexus-Term simmers}: ennuii i, E" i ANKFormoN-TfiE-imm iroens/r; AND,WILLY EICl-IHOLZ, or MANNHEIM, enmrenmnssrenons ro GENERAL ANI'LINEWORKS, INCL, on NEW YORK, A ooBPoBA'rroi oF DELAWARE f PREPARATION onyer nYnsTun't IsoMEe-s on I THE 1.4.5.8,1JAPHTHOYIZENE.

meniiziiripnzonsunmsnun riznrnonno'r No Drawing. Application filed April4,. 1930; Seria1 110.441,?12, and in Germeny ApriI 15, 1929.

.In the U. s. Patent No. 1,5ee,451 there'isde s'cribed'i process whichcomprisescondensing' an 1.4 .5.8-11ephthalenetetrzi oairboxylio acidcompound with an ortho-dierninecompound;

The products'thus robtaineble ere valuable dyestufisyalthough they-erenot oiqun-iforina I constltution, but rather represent mixtures ofisolneriodyestufi's. 'VVh'en condensing, for

instance, 1.4.5.8-naphthilene-tetra carboxylic acid with Vortho@henylenediemine a mixture 7 t of the two isomeric dyestuiis ofthefollowing formulae is obtained. When condensing a substituteortho-phenylene' diemi ne withf1.4i5.8+naph; thalenetetra-carboxylioacid in many. cases thesame holds true, i. e. thereis likewise ob taineda mixture of the twois'omers;

" The presentinvention'relates to a process of separating the; dyestuiimixtures, obtein able according to U. S. PatentNo'. 1,588,451

into their two eomponents Another object j of our invention are thepurified dyestuffs) obtainable according to our new process.

We have now found that the sepa'rationof the dyestuff mixturesobtainable according to U. S. Patent No. 1,588,451 can be effected withture in concentrated. sulfuric acid and causing the dissolveddyestuffs'to fractionally crystallize from the sulfurioucid solution byeither diluting or cooling the sulfuric acid solution. In the exampleshereafter 'following our process and the properties of the dye stuffsobtainable therebyare more fully de} scribed, the parts'areby weight: 7i

(Tl) parts of the isomeric mixture of furic acid of 66 B.,'whilestirring} To thiss 1.4.5.8 naPhthOylene dibenzimida zolf f th le eermulaecf r, y

(obtainable by condensing -1'.4:-;5.empi1uiag lene'tet-ra-cerbox'ylicjacid with 2 mols" of; Y c I ortho-phenylenediamine according to Us S."f Patent No. 1,588,451)s 'are dissolved in sulsolution is graduallyadded," while stirring and cooling, such a quantity of ice, that the j ctemperature of the solutionfduringthe intro duction of the ice does notexceed30 6:"35

C until the precipitatio 1y soluble orange: part of the mixture" is con-1, pl'ete. Thesulfste whichhas been"preoipitated :is filteredfbysuction by, nieansof filterstone,' glass beads oruasbesto'sf The solid lmetterfis then decomposed with ice, the dye-w stud isfiltered bysuction, washed untihn'eu trill and dried. [It is an-orangere'd powder 1the following formula:

and dissolves in monohydr'ate to e brownish .0 i

nofthe niorediflicult v properties.

' :1 ;(2) .l1IIi dflHIni ture oi -{160 partsofsulfuric -w I v V 'hasthe,same properties as that obtainable 7 it V V accordingtoExaniple 1. Fronthesulfuric; 'J

' by drop, while stirring, until theprecipita-sl 1i f tionpf thecomponentyieldinghorange dyeingsis finished. Thefprecipitate is filteredor I i solution. It dyes cotton in an olive Vat very B'., decompo'sedwith'waterg iwashed until; i 7' brilliant orange" tints ofexcellent'fastness neutral and dried, It dyes cotton orange Thesulfuricacid filtrate 'is poured on 'ice F roin the" mother liquor there isobtained 1 K 5 and worked up i'nYthe manner abovede by precipitationwith water thecomponent 76'- scribed The deep red dyestuil thus obtainofthe'dyestuffmixture yielding bluish red I 7 ablewhich hastheifollowingformul'a; tints. '7 7' i 3 p "l v'lhefprocess' whichcomprises dissolving] 7 V I a such a dyestufi' mixture as isobtainableby 1 J condensing a 1.4.5;8-naphthalene-tetra-car lboxylicacid compound with an'ortho-diamine compound, in concentrated,sulfuricacid and f p .fsubjectingthe' solution toga fractional cry'si ftallization .,j. r v 5 -f V a I s 112119 process-which comprisesdissolving j i v lsuch ajdy'estufi'inixture' asisfobtainabl'e by 7 fcondensing a 114.548 naphthalene-tetra' car f boXylic acid con poundwith anorthodia-mine 1 j .qcoinpound, in'concentratedfsulfuric acidfofff o Q g f 166 Bflwhile heating to agtemperature of ab0ut,90 C. C.,cooling down the solu-' tion filtering and treating the-filtrate as well{dissolves in concentratedsulfuri'c'acid to a'redr vasithe'resldue w teI 's0luti0n and'dyescotton in an olive vat bluish 1 anewproduct t dy frl '90 "red tints of very good fastness properties. i w g m L v i gQIncase thedye'stufi mixtureshave not been is completelyseparated, theprocess can bere 'peatedh 7 'acid'ofz669 B. and-{impartsofsulfuric-acid7 bfGOf-B, there are-introducedQOpaPtsof gthe' startingvmaterial usedaccording'to EX- j ample 1." Thewhole-is heated for afshort ,-time toabout 90" and. allowed to cool while stirring The precipitated dyestufiafter standingiora prolonged time, is file 'tered by'suction,"washed-and decomposed with 'water. .It is anrorange product'which 7 i Qacid inother liquorgthere isobtainable"by Z precipitation-withl waterthe corrospon ding formlng inzthe drystate' 'a deepvre'd powd e i i' redproduct giving'analkalinehydrosulfite dlssolvlng in concentratedsulfuricacid'withr vat'fronifwhich cottonis dyed redtints which a red color anddyeing cotton from'anfolivejiis i when" the material is eXposeldjte theair, f coloredyat red shades h'aving a bluish -tintfi M ifbh'angeto'bluislrredtintsgofvery good fast andpossessingsexcellentfastnessproperties. i I

" ness properties;

By mixing the ingredients in 'apr0p0rti0ntures. o V Z V A I; V b1 otherthan that above indicated, for-instance; Y c WILHELM' ECKERD; 5 11 iusing'l 30 parts of sulfuricacid of 66 B. 1 I 3 7 HEINRICH'Z GREUN-E, jw V and partsof GO B; orlOO parts of 60 V WILLY' EICHI-IOLZ a v V VB.jand lOOparts of, 669 B.;or onlysulfuric' 1 acid of 66- BQ, "thedyestufi mixtures are 5 likewise separated finto a 7 component dyeing[orange tints and into a coniponent dyeing i bluish'red tints. v I, 1 20parts of thest arting material used j a cording to Example-laredissolvedin the v p i i cold lin"50parts ofchlorosulfonic acid and 7' 1 5 .jfiiby-jsugtion; washed withsulfuric aud or; 6Q?"

